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US3000762A - Process for reacting polymeric materials with sulfones and products resulting therefrom - Google Patents

Process for reacting polymeric materials with sulfones and products resulting therefrom Download PDF

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Publication number
US3000762A
US3000762A US5177860A US3000762A US 3000762 A US3000762 A US 3000762A US 5177860 A US5177860 A US 5177860A US 3000762 A US3000762 A US 3000762A
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United States
Prior art keywords
sulfone
starch
sulfones
water
grams
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Expired - Lifetime
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English (en)
Inventor
Giuliana C Tesoro
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JP Stevens and Co Inc
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JP Stevens and Co Inc
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Publication date
Priority to NL267024D priority Critical patent/NL267024A/xx
Application filed by JP Stevens and Co Inc filed Critical JP Stevens and Co Inc
Priority to US5177860 priority patent/US3000762A/en
Priority to US3574521D priority patent/US3574521A/en
Priority to DEST17937A priority patent/DE1293720B/de
Priority to GB2905961A priority patent/GB985318A/en
Application granted granted Critical
Publication of US3000762A publication Critical patent/US3000762A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
    • C07D213/20—Quaternary compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/10—Crosslinking of cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/44—Preparation of metal salts or ammonium salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
    • D06M13/272—Unsaturated compounds containing sulfur atoms
    • D06M13/278—Vinylsulfonium compounds; Vinylsulfone or vinylsulfoxide compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31971—Of carbohydrate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2402—Coating or impregnation specified as a size

Definitions

  • the present invention relates to novel chemical processes for modifying the solubility properties of polymeric materials, and more specifically for increasing the water resistance of non-cellulosic water sensitive polymers containing a plurality of hydroxyl groups per polymeric molecule such as starch, polyvinyl alcohol, partially saponified polyvinyl esters and the like.
  • This invention also relates to the insolubilized products resulting from the above modification.
  • this invention also relates to a process for producing said insolubilized products in situ on fabrics and to the products resulting therefrom.
  • divinyl sulfone is as extremely toxic chemical whether taken orally or by absorption through the skin. It causes severe burns when in contact with the skin. It is a powerful lachrymator and vesicant. It is a liquid of relatively high vapor pressure, and therefore difficult to handle (as, for example in weighing). At alkaline pH (above 9.0), it reacts readily with water, so that alkaline solutions of divinyl sulfone have very limited stability.
  • the sulfones of our invention have oral toxicity 20 to 100 times lower than that of divinyl sulfone. They do not act as lachrymators or VSiC3lHtS, and do not cause burns when in contact with the skin. They are solids, or. liquids of extremely low vapor pressure, and can easily be handled in laboratory or mill operations. They exhibit excellent stability in aqueous solutions.
  • a further object of this invention is to provide new and useful polymeric materials which are prepared by reacting certain polymeric materials containing a plurality of hydroxyl groups per polymeric molecule with selected sulfones.
  • a further object of this invention is to provide a novel process for imparting a durable size to a fabric.
  • a further object of this invention is to provide a novel sized fabric as a result of the aforementioned process for imparting a durable size to a fabric.
  • a wa er 501th ice 2 ble polymer containing hydroxyl groups is rendered insoluble by reacting it in the presence of an alkaline catalyst with a sulfone represented by the general formula Ill ll" where R, R, R", and R' are selected from the group consisting of hydrogen and methyl, and Y represents a polar residue derived from a reagent of weak neucleophilic character such as the cation of a weak base (e.g. NC H pyridinium) the anion of a strong acid (e.-g. -SSO Na, thiosulfate; -OSO Na, sulfate), and the like.
  • Nucleophilic character is defined as the tendency to do nate electrons or share them with a foreign atomic nucleus (Gilman-Organic Chemistry, second edition, vol. II, p. 1859).
  • the polymers suitable for the process of the present invention may be natural (e.g. starch) or synthetic (e.g. polyvinyl alcohol, partially saponified polyvinyl acetate and the like).
  • synthetic polymers they may be used in the form of bulk resin, film, fiber, yarn or fabric.
  • starches which may be used are the cereal starches such as corn starch, rice starch, wheat starch and the like; the root starches such as potato starch, tapioca starch and the like, as well as the starches derived from stems, fruits and seeds.
  • amylose (soluble in cold water) and the amylopectin (insoluble in cold water) fractions of raw starch are operative, and the partial degradation products of starch (generally termed dextrins) are also operative.
  • the latter are polymeric products obtained from starch by heating, by partial acid or base hydrolysis, or by enzymatic hydrolysis.
  • Chemically modified starches where part (not more than about 50%) of the hydroxyl groups have been acetylated, etherified or otherwise substituted are also operative.
  • polyvinyl alcohol derivatives which may be used are the polyvinyl alcohol resins derived by partial or total hydrolysis of polyvinyl acetate (marketed for example under the trade name of Gelvatol by the Shawinigan Resin Corp., under the trade name of Elvanol by E. I. du Pont de Nemours, and the like), polyvinyl alcohol fibers and yarns (marketed for example under the trade name of Vinal by the Air Reduction Chemical Co.) either unmodified of the hydroxyl groups are free and unsubstituted) or where part of the hydroxyl groups (not more than about 50%) have been reacted to form acetals, esters, others or other substituted products.
  • Saponified copolymers of organic vinyl esters with other monomers for example vinyl chloride, acrylate esters, acrylonitrile, styrene and the like
  • Z is selected from the groupconsisting of Q SQ and S Qg-, and M s an al ali mg fil selected from the group consisting of sodium, potassium, lithium, and the like. It will be evident that in Formula 2, Z-M corresponds to Y of Formula 1.
  • R, R, R" and R have the same meaning as in Formula 1;
  • R R and R are substituents such as alkyl, aryl, and alkaryl groups of a tertiary amine having an ionization constant lower than about and
  • X is a negatively charged ion derived from an inorganic acid such as hydrochloric, sulfuric, nitric, and the like or from an organically substituted inorganic acid such as *methanesulfonic, benzenesulfonic, and the like.
  • hydrochloric acid is given by way of example only since halogen acids in general can be employed.
  • sulfones encompassed by Formula 1 include those corresponding to the following structure:
  • R, R, R", R', and X have the same meaning as in Formula 3 above and Q is part of a heterocyclic ring of which the nitrogen atom in the formula is also a part such as in pyridine, isoquinoline, alkyl pyrrolidine, and the like.
  • the amount of sulfone which is required to produce the desired effect in the process of the present invention varies widely, depending on the structures of the polymer and sulfone which are reacted, and on the extent of modification which is desired.
  • the amount of sulfone employed may be as low as 3% and as high as 200%, based on the weight of the polymer.
  • the alkaline catalyst is generally a strong base.
  • the phosphates, carbonates, hydroxides and alkoxides of alkali metals, and the quaternary ammonium hydroxides are preferred catalysts.
  • the amount of catalyst em- 'ployed may be varied between wide limits, and depends on the specific base which is selected, on the time and temperature of reaction, and on the nature of the polymer.
  • the concentration may be varied between 0.1% and 30%, based on the weight of solution, with the reaction time varying from several hours to a few seconds at room temperature as the concentration of sodium hydroxide is increased.
  • the inert solvent or dispersion medium used for carrying out of the reaction between the sulfone compound and the polymer can be water or a non-reactive organic compound plus mixtures thereof.
  • the reaction can take place at sub-atmospheric, atmospheric or super-atmospheric pressure, but preferably atmospheric pressure is employed.
  • the reaction can be carried out on the polymer itself, as in the case of polyvinyl alcohol fiber, yarn, fabric and the like. It can be carried out also on an aqueous solution or suspension of the polymer. On the other hand, it can be carried out upon yarn or fabric whichhas been sized with a polyvinyl alcohol or starch derivative. 'In the latter case, the sizing material is insolubilized in situ, and
  • Example 2 The procedure of Example 1 is repeated using 8.8 grams of a 25% sodium hydroxide solution. The polymer obtained is identical with that of Example 1 and is insoluble in boiling water.
  • Example 3 Sixty-two grams of a 7% solution of polyvinyl alcohol (obtained by total hydrolysis of polyvinyl acetate-product marketed as Gelvatol 1-60 by the Shawinigan Resin Corp.) are mixed with 0.3 gram-of a 25% solution of the sulfone used in Example 1. Upon adding 0.2 gram of a 25% solution of sodium hydroxide an insoluble polymer precipitates which is filtered, washed and dried. This product is insoluble in boiling water.
  • polyvinyl alcohol obtained by total hydrolysis of polyvinyl acetate-product marketed as Gelvatol 1-60 by the Shawinigan Resin Corp.
  • Example 5 Forty-four grams of a 10% aqueous solution of partially saponified polyvinyl acetate (Gelvatol 40.10) are mixed with 18.4 grams of the sulfone compound .y CHaGHzNCsHg CHzCHaIlTCsHs at room temperature. A clear solution is obtained. When 32 grams of 25% NaOH are added to this solution, an insoluble gel precipitates out. After filtering, washing anddrying this gel is tested for water resistance. A one gram sample of the gel is treated with 25 cc. of boiling water for 5 minutes, filtered, dried and weighed. No weight loss is observed, proving the excellent water resistance of the product prepared.
  • Gelvatol 40.10 partially saponified polyvinyl acetate
  • Example 6 The procedure of Example 5 is repeated, except that the partially saponified polyvinyl acetate (Gelvatol 40-10) is replaced with completely hydrolyzed polyvinyl acetate (Gelvatol 1-60). Results similar to those observed with Example 5 are obtained.
  • a test portion of the solid product (1 gram) is suspended in 10 grams of water and the water is brought to a boil.
  • the modified starch product swells slightly, while the untreated starch forms a thick gelatinous mass when tested by the same procedure.
  • Example 8 The procedure of Example 7 is repeated using 47 grams of a 25% solution of the sulfone of Example 1. By so increasing the amount of sulfone reactant, the modified corn starch which is obtained can be boiled with water without rupture of the individual starch particles and without increase in the viscosity of the aqueous solution.
  • Example 9 The procedure of Examples 7 and 8 is repeated, replacing the 150 grams of corn starch with 75 grams of a cold water soluble starch marketed under the trade name Kosol by the National Starch and Chemical Co. This starch which is completely soluble in cold water is rendered insoluble in water even at the boil after reaction with the sulfone of Example 1.
  • Example 10 When the procedure of Example 7 is repeated using 10 grams of the sulfone of Example 5, the properties of the product obtained are identical to those of the product of Example 7. By increasing the amount of sulfone to 45 grams, the insolubilization of the starch is as complete as that observed in Example 8. It is thus apparent that the degree of swelling of starch particles in water can be varied almost at will by varying the concentration of sulfone reagent used in the treatment.
  • Example 11 Samples of yarn manufactured from unmodified polyvinyl alcohol fiber (non-heat treated, yarn size 25/ 1) are impregnated with an aqueous solution containing 250 grams per liter of the sulfone compound CHzCHaSSOaNB.
  • the yarn is passed through the squeeze rolls of a laboratory padder, adjusting the pressure of the rolls so as to give a wet pickup of about 75%.
  • the uptake of sulfone is thus about 18 grams per 100 grams of yarn.
  • the yarn so treated is dried, then passed through a 10% potassium hydroxide solution, squeezed through the rolls of the padder and allowed to stand at room temperature for 30 minutes. It is then washed in dilute acetic acid and water, and dried.
  • the yarn so treated is insoluble in boiling water, while the untreated yarn is gradually dissolved when immersed in water at 70-80 C.
  • Example 12 Samples of cotton fabric are treated with solutions of the following compositions, passed through the rolls of a laboratory padder set to give about 70% wet pickup, and dried:
  • fabrics besides cotton can be treated in this manner.
  • fabrics manufactured from regenerated cellulose, polyamide, polyester and acrylic fibers can be so treated if a stiff finish which is durable to laundering is desired.
  • a process for insolubilizing non-cellulosic natural and synthetic polymers containing a plurality of hydroxyl groups per polymeric molecule by reacting said polymers in the presence of an alkaline catalyst with a sulfone corresponding to the formula where R, R, R", and R' are selected from the group consisting of hydrogen and methyl and Y is a polar residue derived from a reagent of weak nucleophilic character.
  • a method of imparting to a fabric a durable sizing material comprising impregnating said fabric with a non-cellulosic polymer containing a plurality of hydroxyl groups per polymeric molecule and thereafter insolubilizing said polymer on said fabric by reacting said polymer in the presence of an alkaline catalyst with a sulfone corresponding to the formula RI! R!!! where R, R, R", and R" are selected from the group consistingof hydrogen and methyl and Y is a polar residue derived from a 'reagent'of weak nucleophilic character.
  • a fabric comprising the reaction product resulting from impregnating a fabric with a non-cellulosic polymer containing a plurality of hydroxyl groups per polymeric molecule and thereafter insolubilizing said polymer on said fabric with a sulfone corresponding tothe'formula f f 2,524,399 Schoene et a1. Oct. 3, 1950 00 Schoene et a1. Oct. 3, 1950 9,704 Schoeneet a1. Jan. 30, 1951

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Biochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
US5177860 1960-08-25 1960-08-25 Process for reacting polymeric materials with sulfones and products resulting therefrom Expired - Lifetime US3000762A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
NL267024D NL267024A (pt) 1960-08-25
US5177860 US3000762A (en) 1960-08-25 1960-08-25 Process for reacting polymeric materials with sulfones and products resulting therefrom
US3574521D US3574521A (en) 1960-08-25 1961-01-03 Modification of cellulosic textile materials with divinyl sulfone precursors
DEST17937A DE1293720B (de) 1960-08-25 1961-06-10 Verfahren zur Verbesserung der Eigenschaften von aktive Wasserstoffatome tragenden Polymeren in Form von Textilgut
GB2905961A GB985318A (en) 1960-08-25 1961-08-11 Improvements in or relating to polymeric materials

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Application Number Priority Date Filing Date Title
US5177860 US3000762A (en) 1960-08-25 1960-08-25 Process for reacting polymeric materials with sulfones and products resulting therefrom
US7998861A 1961-01-03 1961-01-03

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US3574521D Expired - Lifetime US3574521A (en) 1960-08-25 1961-01-03 Modification of cellulosic textile materials with divinyl sulfone precursors

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Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3194678A (en) * 1960-12-20 1965-07-13 Eastman Kodak Co Polymers cross-linked with sulfur dioxide, fabrics coated therewith, and coating method
US3226395A (en) * 1960-10-04 1965-12-28 Hoechst Ag Water-insoluble phthalocyanine dyestuffs and process for their manufacture
US3236860A (en) * 1959-04-24 1966-02-22 Hoechst Ag Water-soluble phthalocyanine dyestuffs containing thiosulfuric acid groups
US3240797A (en) * 1959-12-31 1966-03-15 Deering Milliken Res Corp Bis (sulfatoethyl) sulfoxide salts
US3249394A (en) * 1960-12-06 1966-05-03 Ciba Ltd Vat dyeing with thiosulfate dyes
US3251642A (en) * 1960-02-23 1966-05-17 Tootal Broadhurst Lee Co Ltd Halo-, sulfato-, and phosphato-alkyl sulfonium salts reactions with hydroxylated and aminated textiles and other polymers and the product of such reactions
DE1227419B (de) * 1962-09-19 1966-10-27 Hoechst Ag Verfahren zur Verbesserung der Knitterfestigkeit von Textilmaterialien
US3314744A (en) * 1961-07-03 1967-04-18 Gen Aniline & Film Corp Crosslinkage of cellulose fibers with phosphate esters of di-ethanol sulfones
US3338883A (en) * 1961-03-31 1967-08-29 Stevens & Co Inc J P Process for modifying polymeric materials, and modifier reactants for such use
US3338661A (en) * 1964-10-28 1967-08-29 Dow Corning Cellulosic fabrics rendered crease resistant and water repellant through treatment with compositions comprising catalyst-water repellant silicones and sulfone crosslinking agents
US3341279A (en) * 1961-05-22 1967-09-12 Gen Aniline & Film Corp Modification of reactive hydrogenand halogen-containing materials with thioxane dioxide
US3350162A (en) * 1963-01-28 1967-10-31 Staley Mfg Co A E Method of creaseproofing and stiffening cellulose textile with dimethylol ethylene urea and amylopectin size
US3359061A (en) * 1961-12-19 1967-12-19 Clark M Welch Process for making alkoxyethylsulfonylethyl ethers of cellulose
US3414367A (en) * 1963-11-06 1968-12-03 Agriculture Usa Process for making n-substituted aminoethylsulfonylethyl ethers of cellulose
US3477802A (en) * 1963-03-19 1969-11-11 Stevens & Co Inc J P Modification of cellulose,polyvinyl alcohol and starch with compounds characterized by ethylene radicals having an electron attracting group which stabilizes carbanions on one carbon atom thereof and an alkoxy or hydroxy group on the other
US3501260A (en) * 1964-03-18 1970-03-17 Stevens & Co Inc J P Polyvinyl alcohol and starch bound to cellulosic textile substrate through reaction with beta-oxyethyl sulfones
US3506711A (en) * 1963-08-13 1970-04-14 Stevens & Co Inc J P Sulfonamide compounds
US3615790A (en) * 1967-04-27 1971-10-26 Fmc Corp General dye-assist for synthetic fibers
EP0070143A1 (en) * 1981-07-08 1983-01-19 Monsanto Europe S.A./N.V. Organic thiosulphates and thiosulphonates useful as stabilising agents for rubber vulcanisates

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4240943A (en) * 1978-02-27 1980-12-23 Dainichiseika Color & Chemicals Mfg. Co., Ltd. Textile finishing composition

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2524400A (en) * 1949-03-31 1950-10-03 Us Rubber Co Chemically modified starches
US2524399A (en) * 1948-07-07 1950-10-03 Us Rubber Co Cellulose treated with di-vinyl sulfone to shrinkproof
US2539704A (en) * 1948-07-07 1951-01-30 Us Rubber Co Treatment of hydroxylated polymers

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3218118A (en) * 1958-07-23 1965-11-16 Rohm & Haas Crease-proofing cellulosic fabrics, the fabrics obtained and methods of making them
BE586605A (pt) * 1959-01-17
BE598593A (pt) * 1959-12-31
GB899902A (en) * 1960-04-29 1962-06-27 Deering Milliken Res Corp Process for treating cellulosic textile materials

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2524399A (en) * 1948-07-07 1950-10-03 Us Rubber Co Cellulose treated with di-vinyl sulfone to shrinkproof
US2539704A (en) * 1948-07-07 1951-01-30 Us Rubber Co Treatment of hydroxylated polymers
US2524400A (en) * 1949-03-31 1950-10-03 Us Rubber Co Chemically modified starches

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3236860A (en) * 1959-04-24 1966-02-22 Hoechst Ag Water-soluble phthalocyanine dyestuffs containing thiosulfuric acid groups
US3240797A (en) * 1959-12-31 1966-03-15 Deering Milliken Res Corp Bis (sulfatoethyl) sulfoxide salts
US3251642A (en) * 1960-02-23 1966-05-17 Tootal Broadhurst Lee Co Ltd Halo-, sulfato-, and phosphato-alkyl sulfonium salts reactions with hydroxylated and aminated textiles and other polymers and the product of such reactions
US3226395A (en) * 1960-10-04 1965-12-28 Hoechst Ag Water-insoluble phthalocyanine dyestuffs and process for their manufacture
US3249394A (en) * 1960-12-06 1966-05-03 Ciba Ltd Vat dyeing with thiosulfate dyes
US3194678A (en) * 1960-12-20 1965-07-13 Eastman Kodak Co Polymers cross-linked with sulfur dioxide, fabrics coated therewith, and coating method
US3338883A (en) * 1961-03-31 1967-08-29 Stevens & Co Inc J P Process for modifying polymeric materials, and modifier reactants for such use
US3341279A (en) * 1961-05-22 1967-09-12 Gen Aniline & Film Corp Modification of reactive hydrogenand halogen-containing materials with thioxane dioxide
US3314744A (en) * 1961-07-03 1967-04-18 Gen Aniline & Film Corp Crosslinkage of cellulose fibers with phosphate esters of di-ethanol sulfones
US3359061A (en) * 1961-12-19 1967-12-19 Clark M Welch Process for making alkoxyethylsulfonylethyl ethers of cellulose
DE1227419B (de) * 1962-09-19 1966-10-27 Hoechst Ag Verfahren zur Verbesserung der Knitterfestigkeit von Textilmaterialien
US3350162A (en) * 1963-01-28 1967-10-31 Staley Mfg Co A E Method of creaseproofing and stiffening cellulose textile with dimethylol ethylene urea and amylopectin size
US3477802A (en) * 1963-03-19 1969-11-11 Stevens & Co Inc J P Modification of cellulose,polyvinyl alcohol and starch with compounds characterized by ethylene radicals having an electron attracting group which stabilizes carbanions on one carbon atom thereof and an alkoxy or hydroxy group on the other
US3506711A (en) * 1963-08-13 1970-04-14 Stevens & Co Inc J P Sulfonamide compounds
US3414367A (en) * 1963-11-06 1968-12-03 Agriculture Usa Process for making n-substituted aminoethylsulfonylethyl ethers of cellulose
US3501260A (en) * 1964-03-18 1970-03-17 Stevens & Co Inc J P Polyvinyl alcohol and starch bound to cellulosic textile substrate through reaction with beta-oxyethyl sulfones
US3338661A (en) * 1964-10-28 1967-08-29 Dow Corning Cellulosic fabrics rendered crease resistant and water repellant through treatment with compositions comprising catalyst-water repellant silicones and sulfone crosslinking agents
US3615790A (en) * 1967-04-27 1971-10-26 Fmc Corp General dye-assist for synthetic fibers
EP0070143A1 (en) * 1981-07-08 1983-01-19 Monsanto Europe S.A./N.V. Organic thiosulphates and thiosulphonates useful as stabilising agents for rubber vulcanisates

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US3574521A (en) 1971-04-13
GB985318A (en) 1965-03-10
NL267024A (pt) 1900-01-01
DE1293720B (de) 1969-04-30

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